JPS5941651B2 - Method for producing polybutene-1 - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polybutene-1, and more specifically, in obtaining highly stereoregular polybutene-1, the catalyst activity decreases little even at high polymerization temperatures, and the catalyst can be easily removed. The present invention relates to a process for producing polybutene-1 using a novel catalyst system with sufficiently high activity that it is not necessary.

Conventionally, many proposals have been made regarding catalysts for producing highly stereoregular polymers of α-olefins containing butene-1, but the most well-known one is the use of solid titanium halides and dialkylaluminum halides. It is a catalyst system consisting of an organoaluminum compound such as

However, although these catalyst systems produce highly stereoregular polymers, their polymerization activity is not sufficiently high, and therefore a step is required to remove desolvation residues remaining in the resulting polymers.

As a solution to this problem, various methods have been developed in recent years that dramatically improve the polymer yield per transition metal and solid catalyst component by immobilizing transition metal compounds on carriers, making it possible to substantially omit the catalyst removal step. A method is proposed. As one of the methods, the present inventors reacted a reaction product of a specific silicon compound with a Gerignard reagent and a halogen compound of aluminum and/or silicon with a halogen compound of titanium in the presence of an organic acid ester. We proposed the use of a catalyst consisting of a solid catalyst component obtained by the process, an organoaluminium compound, and an organic acid ester. (Japanese Patent Application No. 53-112488) As a result of further studies, the present inventors found that the above catalyst system has sufficiently high activity and can produce polyolefin with high stereoregularity in high yield; When used in the polymerization of butene-1, as the polymerization temperature rises, the activity of the catalyst decreases significantly, and especially when the polymerization temperature rises to 60°C or higher, this tendency becomes gradually more pronounced, and the polymer production efficiency per catalyst deteriorates. It has become clear that this phenomenon occurs.

As a result of extensive research to solve the above-mentioned difficulties, the present inventors have found that two specific types of organoaluminum compounds are used as the organoaluminum compound components of the catalyst system proposed above in the polymerization of butene-1, and A catalyst system with a molar ratio within a specific range has a small decrease in activity at high polymerization temperatures, can increase the polymer production efficiency per catalyst, and can produce polybutene-1 with extremely high stereoregularity. The present inventors have discovered the fact that the present invention can be obtained, and have completed the present invention.

4-a-b That is, the present invention is RlaHbSiO? (However, R1 is selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an alloxy group, a is an integer of 0, 1, or 2, b is an integer of 1, 2, or 3, and a+b≦3) The reaction product (a) of a linear or cyclic hydropolysiloxane having a structural unit represented by
In the formula, R2 represents a hydrocarbon group having 1 to 12 carbon atoms, M represents an aluminum atom or a silicon atom, z represents its valence and is a number of 3 or 4, X represents a halogen atom, and n represents O~
Represents the number of (z-1).

A reaction product (b) obtained by reacting one or more compounds represented by (b) with one or more titanium halogen compounds in the presence of an organic acid ester. solid catalyst component, tolualkylaluminum compound 8, organic acid ester [, and general formula R3jTlA-Ct3-m (wherein R3 has 1 carbon number)
~8 hydrocarbon groups, 0 cm × 3. ) When producing polybutene-1 using a catalyst consisting of an organoaluminum compound (self) represented by (self), the molar ratio between the organoaluminum compound (self) and the trialkylaluminum compound is within the range of 0.1 to 10. The present invention relates to a method for producing polybutene-1, which is characterized by the following. When butene-1 is polymerized using the catalyst according to the method of the present invention, as mentioned above, even at a high polymerization temperature, for example, at a polymerization temperature of 60 C, the decrease in catalyst activity is small, and a high polymer production per catalyst is achieved. Gain efficiency. Therefore, since the yield of polybutene-1 per titanium atom and the yield of polybutene-1 per solid catalyst component are extremely high, titanium halogen compounds in the obtained polymer can be obtained without performing expensive operations such as catalyst removal. Furthermore, the present catalyst system has the advantage of providing polybutene-1 with much higher stereoregularity than the previously proposed methods.

Furthermore, since this catalyst system is sensitive to a small amount of a molecular weight regulator such as hydrogen, it is extremely easy to control the molecular weight of the resulting polymer, and a wide variety of grades can be produced.
Particularly when hydrogen is used, both the catalyst activity and the stereoregularity of the polymer are improved. Furthermore, the method for producing a solid catalyst component according to the present invention involves reacting the reaction product (a) of a hydropolysiloxane and a Grignard reagent with an aluminum compound or a silicon compound, and then converting the obtained reaction product into an organic acid ester. The manufacturing method of the solid catalyst component is simple, as it only requires reacting titanium with a halogen compound in the presence of a halogen compound, and it also has the advantage of being able to easily produce a solid catalyst component of constant quality with good reproducibility. , its industrial value is extremely large. The method of the present invention will be explained in more detail below.

The solid catalyst component used in the present invention is usually prepared as follows. First, the hydropolysiloxane used in the production of the reaction product (a) in the present invention has the following general formula 4-a-b RlaHbSiO? (However, R1 is 1 selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an alloxy group.
It is a valent organic group, a represents 0, 1 or 2, b represents 1, 2 or 3, and a+b≦3.

) A chain or cyclic hydropolysiloxane having a structural unit shown in the following formula, a compound of any degree of polymerization, or a mixture thereof, and having a low viscosity liquid with a low degree of polymerization and a viscosity of 100,000 centistokes at 25°C. Grease-like or wax-like products with various degrees of polymerization,
Further examples include solid ones.

Although the structure of the terminal group of this hydropolysiloxane does not significantly affect the activity, it may be capped with any inert group, such as a tonialkylsilyl group.

Specific examples include tetramethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane,
Examples include tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane, and chlorophenylhydropolysiloxane. The Grignard reagent used in the production of the reaction product (a) in the present invention has the general formula (MgRl) obtained by the reaction of a halogen-containing organic compound and metallic magnesium.
p.(R4MgX)q (However, R4 represents a hydrocarbon group, X represents a halogen atom, and p and q represent a number from O to 1, and have the relationship p+q21.

), an ether complex thereof, or a mixture thereof, and for example, p is 0. R4 where q is 1
The so-called Grignard reagent p in the narrow sense, denoted by MgX
dihydrocarpylmagnesium represented by RCMg where is 1 and q is 0, other (MgRdi)p.
X) various organic magnesium halides represented by q,
These include ether complex compounds or mixtures thereof. These Grignard reagents are prepared by conventionally known methods.
For example, it can be easily synthesized in an ether solvent such as diethyl ether, dibutyl ether, or tetrahydrofuran, or in a hydrocarbon solvent such as heptane, octane, benzene, or toluene in the presence of an appropriate amount of a complexing agent such as an ether or an amine. The reaction product (a) used in the present invention can be easily obtained by reacting the hydropolysiloxane represented by the above formula with a Grignard reagent by any method.

For example, the reaction between a hydropolysiloxane and a Grignard reagent can be carried out by adding the hydropolysiloxane little by little to a Grignard reagent synthesized in an appropriate solvent with stirring, and then heating the mixture for a predetermined period of time after adding the entire amount.

This reaction proceeds at room temperature with a strong exotherm, but in order to complete the reaction, the reaction mixture must be heated at 50 to 10°C.
It is preferable to heat for 1 to 5 hours. However, this operation is not always necessary. The charging ratio of hydropolysiloxane and Grignard reagent is preferably such that the molar ratio of MgR4:Si is 0.05 to 1:1.
The reaction product Ua) thus obtained can be used as a reaction mixture in the production of the reaction product (b) in the present invention, but if it contains a large amount of ethers derived from the Grignard reagent, unfavorable results may occur. Generally, some or all of the solvent is removed from the reaction mixture containing reaction product (a), and the reaction product (b) is dissolved or suspended in an inert hydrocarbon solution.
).

However, this reaction product (a) has the property of being soluble in aromatic hydrocarbon solvents such as toluene. Therefore, in order to produce the reaction product (b) smoothly and with good reproducibility, and to obtain a homogeneous reactive component (b), the reaction product (a) must be dissolved in an aromatic hydrocarbon solvent to form a homogeneous solution. It is preferable to use the reaction product (b) as a reaction product. General formula R2nM (2
2Xz-n (wherein R2 represents a hydrocarbon having 1 to 12 carbon atoms, M represents an aluminum atom or a silicon atom, z represents the valence and represents the number 3 or 4, X represents a halogen atom, n represents a number from O to (z-1).

The compound represented by ) is a halogen-containing compound of aluminum or silicon, and includes various compounds based on the type of R2 and the combination of values of N and z. That is, n is O
When R2 is an alkyl group, it is represented by M()Xz and is an aluminum halide or a silicon halide, and when R2 is an alkyl group, it is an alkyl aluminum halide, an alkyl silicon halide, etc. Specific examples of these compounds include aluminum trichloride, aluminum tribromide, aluminum triiodide, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride, etc. Examples of silicon compounds include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane, ethyltrichlorosilane, butyltrichlorosilane, phenyltrichlorosilane, and silicon tetrabromide. Of course, the above compounds represented by the general formula R2nM(Z )Xz-n
It can be obtained by reacting the compound represented by or a mixture thereof.

Although the reaction can be carried out in the presence or absence of an inert hydrocarbon solvent, it is generally preferred to carry out the reaction in the presence of an inert hydrocarbon solvent. In particular, using an aromatic hydrocarbon solvent such as benzene, toluene, etc. as an inert hydrocarbon solvent and using the reaction product (a) as a homogeneous solution of these solvents facilitates the reaction and provides a homogeneous solution. This method is extremely preferable also for the purpose of producing the reaction product (b) with good reproducibility and constant quality, and always obtaining homogeneous solid catalyst component particles with constant quality.

Both can be reacted in any ratio, but R2nM per 1 mol of magnesium in the reaction product (a)
It is preferable to use the compound represented by (Z)Xz-n or a mixture thereof in a proportion of 0.1 to 10 moles. The reaction temperature and reaction time for both can be arbitrarily selected, but -
The temperature is generally 10°C to 120°C for 5 minutes to 20 hours, and particularly preferably 0 to 80°C for 1 to 8 hours.

The reaction product (b) thus obtained may be used as a reaction mixture for preparing a solid catalyst component, or the reaction mixture may be washed with an inert hydrocarbon solvent such as hexane, heptane, kerosene, etc. Only the reaction product (b) which is insoluble in the inert hydrocarbon solvent may be separated and recovered and used for the preparation of the solid catalyst component.

In particular, when an alkyl aluminum halide or the like is used when producing the reaction product (b), the transition metal content in the solid catalyst component increases significantly when preparing the solid catalyst component in the next step. The latter operation is preferable because it becomes difficult to obtain a polymerization catalyst exhibiting catalytic efficiency and the production rate of stereoregular polymers decreases.

In addition, when using the reaction product (b) separated and recovered after washing with an inert hydrocarbon solvent, it should be sufficiently dried by a method such as vacuum drying, or it should be washed in an inert hydrocarbon solvent. Any method may be used as a dispersed product.

Then, the reaction product (b) in the presence of an organic acid ester
The halogen-containing compound of titanium used in the reaction of the halogen compound of titanium and titanium has the general formula TiXt (0R5).
4-t (wherein, X represents a halogen atom, R5 represents a hydrocarbon group having 1 to 8 carbon atoms, and t represents an integer of 1-4.

), and specific examples include TiC
t4, TiBr4Tl(0C2H5)Ct3,Tl(0
C4H,)Ct3,Tl(0C2H5)2Ct2,Ti
(0C3H7)2ct2,Ti(0C4H,)2ct2
etc. The reaction between the reaction product (b) and the titanium-containing halogen compound can be carried out in the presence or absence of an inert hydrocarbon solvent. Although both can be reacted in any ratio, it is preferable to use the halogen-containing titanium compound in a ratio of 0.1 to 150 mol per 1 mol of magnesium in the reaction product (b).

Further, in the reaction of the reaction product (b) with the titanium halogen compound, examples of organic acid esters that are allowed to coexist include aliphatic carboxylic acid esters, aromatic carboxylic acid esters, and aliphatic carboxylic acid esters.

Among these, aromatic carboxylic acid esters are most preferred;
Specific examples include methyl benzoate, ethyl benzoate,
Examples include methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate.

The amount of the organic acid ester used is in the range of 0.1 to 2.0 mol, preferably 0.5 to 5 mol, per 1 mol of Mg atoms in the reaction product (b).

The method for adding the organic acid ester is I) When preparing the reaction product (5), the reaction product (a) and the general formula R2nM(Z)
A method in which the compound represented by Xz-i is added together with Tokichi.

2) A method in which the reaction product (b) is mixed with the titanium halogen compound in advance before the reaction product (b) is reacted with the titanium halogen compound.

3) A method in which a titanium halogen compound is added to the reaction product (b) at the same time as the reaction takes place.

4) A method in which a halogen compound of titanium is added to the reaction product (b) and then added.

Either of these may be used.

The reaction temperature and reaction time between the reaction product (b) and a titanium halogen compound in the presence of an organic acid ester are not particularly limited, but the reaction is carried out at 500C to 150C and for 30 minutes to 20 hours. is common.

In this way, solid catalyst component particles are produced, and the solid catalyst component particles are recovered by washing the reaction mixture with an inert hydrocarbon solvent such as hexane, heptane, kerosene, or the like to remove soluble components.

The solid catalyst component thus obtained is used as a polymerization catalyst for butene-1 together with the trialkylaluminum compound, the organic acid ester, and the organoaluminum compound. If the ratio is kept within a certain range, polybutene-1 with sufficiently high activity and high stereoregularity can be produced, but if necessary this solid catalyst component or the reaction mixture can be further enriched with titanium. A solid component obtained by treating with a halogen compound and washing with an inert hydrocarbon solvent or the like may be used as the solid catalyst component. This method is effective in maintaining a high level of stereoregularity and further increasing activity.

The thus obtained solid catalyst component usually contains 0.5% to 10% by weight of titanium atoms, and the molar ratio of the organic acid ester to titanium atoms in the solid catalyst component is 0.6 to 4.0.
is within the range of This solid catalyst component is dried by dry bombing under reduced pressure or dispersed in an inert solvent for preparing a polymerization catalyst.

Trialkylaluminium compound used in the present invention 5
is the general formula AIR6R7R8 (however, R6, R7 and R8
are hydrocarbon groups having 1 to 8 carbon atoms, and may be different from each other or the same.

) Specific examples of trialkylaluminum compounds include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, etc., and one or more of these may be used in combination.

Furthermore, examples of the organic acid ester 0 include aliphatic carboxylic esters, aromatic carboxylic esters, and alicyclic carboxylic esters.

Among these, aromatic carboxylic acid esters are most preferred;
Specific examples include methyl benzoate, ethyl benzoate,
Examples include methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate.

These organic acid esters may be the same as or different from the organic acid ester used in the production of the solid catalyst component. Furthermore, the organoaluminum compound [as described above, the general formula AIR3mlCt
3-n1 (where R3 is a hydrocarbon group having 1 to 8 carbon atoms, 0x3), and specific examples thereof include dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, Examples include ethylaluminum dichloride, ethylaluminum sesquichloride, dibutylaluminum chloride, dihexylaluminum chloride, and dioctylaluminum chloride, and one or more of these can be used in combination. The butene-1 polymerization catalyst used in the present invention comprises the solid catalyst components listed above, 8 trialkylaluminum compounds, 0 organic acid esters, and 0 organic aluminum compounds. in the presence or absence of an inert hydrocarbon solvent.

There are no particular limitations on the method of bringing these four components into contact, but for example, a catalyst system can be easily formed by simultaneously charging and stirring these four components in the presence of a solvent in a catalyst preparation container or polymerization reactor. You can force it.
In the method of the present invention, when forming the butene-1 polymerization catalyst, the ratio of the trialkylaluminum compound 5 and the organoaluminum compound (self) is the most important, and the molar ratio of the organoaluminum compound 9 and the trialkylaluminum compound 5 ( Hereinafter abbreviated as (self)/target.

) is maintained within the range of 0.1 to 10, thereby achieving the object of the present invention. In other words, (self) / leaf is 0.1
If the amount is lower, the activity of the catalyst will be greatly reduced at high polymerization temperatures, and the effect of the organoaluminum compound (self) will not be fully exhibited.Also, if the molar ratio is higher than 10, the activity of the catalyst will be extremely low. It will drop. In other words,
The object of the present invention cannot be achieved outside the range of I>)/8=0.1 to 10. When polymerizing butene-1 using the catalyst system of the present invention, the molar ratio of the trialkylaluminum compound 8 to the titanium atoms in the solid catalyst component used (hereinafter 8
/T1 for short. ) is preferably within the range of 10 to 80,
The molar ratio of the organoaluminum compound and the titanium atoms in the solid catalyst component (hereinafter referred to as I>) is abbreviated as Ti. ) is 10
The range of 180 to 180 is preferable. Furthermore, the molar ratio of the trialkylaluminum compound 8 and the organoaluminum compound (self) to the sum of the organic acid ester and the organic acid ester 0 contained in the solid catalyst component used (hereinafter referred to as total organic acid ester/8 and total organic acid ester) /Abbreviated as [.

) are 0.1-0.4 and 0.03-0.8, respectively.
It is preferably within the range of . The amount of solid catalyst component to be used is essentially determined by the content of titanium atoms contained in the solid catalyst. For example, 0.1 to 5 T1V in terms of titanium atoms per 1 ton of solvent? , preferably within the range of 0.2 to 2.0.

In addition, the amount of the trialkylaluminum compound and organoaluminum compound (self) to be used is based on the content of titanium atoms in the solid catalyst component used and the amount used.
It is preferable to determine and use the molar ratio within the above range.

When polymerization is usually carried out in an inert hydrocarbon solvent, it is preferable to use 0.1 mm0I or more per ton of solvent.

In addition, the amount of organic acid ester used is determined based on the content and amount of organic acid ester in the solid catalyst component, the amount of trialkyl aluminum compound 8, and the amount of organic aluminum compound (self) used. It is preferable to keep the molar ratio within the range.

In this way, the usage amount of each catalyst component of solid catalyst component, trialkylaluminum compound 8, organic acid ester 0, and organoaluminum compound (self) is determined, but in any case, the amount of the organic aluminum compound (self) and the trialkylaluminum compound (self) are determined. The alkylaluminum compound (6) must be used so that the molar ratio /8 falls within the above range. When a polymerization catalyst is prepared in a polymerization reactor using each of these catalyst components, after the formation of the catalyst, butene-1 is fed into the same vessel, or when a polymerization catalyst is prepared in a separate vessel. In this method, a catalyst suspension was charged into a polymerization reactor, and butene-1
Butene-1 can be easily polymerized by feeding it into the same container.

The polymerization reaction of butene-1 according to the method of the present invention is carried out in the same manner as the polymerization reaction of olefin using a conventional Ziegler-Natsuta type catalyst.

That is, the reaction is conducted in the substantial absence of oxygen and moisture. Polymerization is a polymerization method using a suitable inert hydrocarbon solvent,
A solventless polymerization method or a gas phase polymerization method in a monomer solvent may be employed, and the polymerization method may be a batch method, a continuous method, or any other method. The preferred polymerization temperature is 10 to 100°C,
In particular, the temperature is 30 to 80°C, and the polymerization pressure is 0.5 to 20k.
9/CTil is preferred.

The molecular weight of the polymer obtained by the method of the present invention is determined by the polymerization temperature,
Although it can be adjusted as desired by changing the amount of catalyst used, the most effective adjustment method is to add hydrogen to the polymerization system.

That is, the use of hydrogen improves the catalytic activity and the stereoregularity of polybutene 1, and can be said to be an excellent method for controlling the molecular weight.

In addition to the homopolymerization of butene-1, the catalyst system used in the present invention can also be used for copolymerization with small amounts of any olefin, such as ethylene, propylene, hexene-1, and the like.

As mentioned above, since the polymerization activity of the catalyst system is extremely high, the amount of residual catalyst in polybutene-1 obtained without any catalyst removal operation is extremely small.

As a result, the residual catalyst has almost no negative effect on the quality of conventional polybutene-1, and it has many advantages such as being able to obtain molded products with excellent color tone and strength even when processed as is. Its usefulness is extremely great. The present invention will be described in more detail with reference to Examples below.

Example 1a) Preparation of reaction product (a) of hydropolysiloxane and Grignard reagent A 75 ml solution of n-butylmagnesium chloride in tetrahydrobutene (n-
0.167m01 as butylmagnesium chloride
) was collected, and while stirring, 10.5 ml of methylhydropolysiloxane (viscosity at 25°C of about 30 centistokes) whose ends were capped with trimethylsilyl groups (0 as Si) was collected.
．． 175m01) was gradually added dropwise.

Because it generates heat, the reactor is cooled with a refrigerant until the internal temperature reaches 70℃.
After adding the entire amount, the mixture was kept at 7°C for 1 hour, and then cooled to room temperature to obtain a dark brown transparent solution. A portion of this solution was taken and the method of Gilman et al. (J. Am. c.
hem. sOc. 472OO2 (1925) for the presence or absence of unreacted n-butylmagnesium chloride, it was found that no unreacted n-butylmagnesium chromide was present. The solvent was distilled off under reduced pressure while keeping this solution at 50° C. to obtain 38.69 white solid reaction product (a). The amount of tetrahydrofuran contained in this white solid was 0.44 m01 per Mgl atom. (D determined by gas chromatography after hydrolysis)
b) Production of reaction product (b) The above white solid reaction product (a) 12 was placed in a glass reactor whose interior had been thoroughly dried and purged with nitrogen.

After collecting 59 and dissolving it in 200ml of toluene, Si
Ct42O. 49 was added dropwise to the mixture at 44-60°C over 1.5 hours while stirring.

Thereafter, the reaction was carried out at the same temperature for 1.5 hours. After the reaction, the solid phase was separated and washed four times with 500 ml of n-hexane. This was then dried under reduced pressure at 50°C to obtain 7.29 of a white reaction product (b).

The M9 content in this reaction product (b) 19 is 171 (7
．． 03mm01) Chlorine content 402~(5.74mm0
1), the silicon content was 111 (3.95 mm01).

c) Production of solid catalyst component 9.3f1 of the above white reaction product (b) was collected into a glass reactor whose interior had been thoroughly dried in advance and nitrogen was supplied, and then 75ml of n-hexane and 11benzoic acid were added thereto. ethyl 15
9 was added and suspended for 30 minutes with stirring.

Then, Tict42599 was added and the reaction was carried out under reflux for 2 hours.

After the reaction is complete, the solid content is sufficiently settled and the supernatant liquid is 150ml.
After removing 1, TiCt4l739 was added again and the reaction was further carried out under reflux for 2 hours. After the reaction was completed, the solid phase was separated and washed four times with 500 ml of n-hexane.

Then, drying was performed under reduced pressure at 500C to obtain a solid catalyst component mass of 8.59. The titanium content in this solid catalyst component 19 was 24.0η (0.501mm 01), and the content of ethyl benzoate was 80.5η (0.546mm 01). d) Inner capacity 1 equipped with polymerization reaction stirrer, heating and cooling jackets
．． Dry the inside of a 2t stainless steel autotaleve,
After purging with nitrogen, the autoclave was filled with 600ml of well-purified n-hexane according to a conventional method, 0.15mm of triethylaluminum, 0.75mm of diethylaluminum monochloride, . Methyl P-triylate 0.
044mm01. and the solid catalyst component 16 mentioned above.

7Tf19 (0.00835mm01 in terms of titanium atoms)
) were added sequentially.

(In this example, (1)/Dan=5, and other 8/Ti
-18 (own) / Ti-90, all organic acid esters / publication = 0
．． 35 total organic acid esters/(auto)=0.07.

) Next, after adding 0.10 kg/CTil of hydrogen to the polymerization system, the temperature of the polymerization system was raised to 600 C, and n-butene-1 was introduced, and polymerization was started at a total pressure of 2.5 k9/~. . After polymerization was carried out for 3 hours while keeping the temperature and total pressure constant, the introduction of n-butene-1 was stopped, the reactor was cooled to room temperature, and unreacted n-butene-1 was purged. The contents were poured into a large amount of methanol to obtain a white polymer. After washing, drying under reduced pressure and heating (500C, 5 hours) was performed to obtain 112.99% of a white solid polymer. The polymer production rate per 19 titanium atoms of this catalyst is 282.3k9/9Ti. Meanwhile, this polymer was dissolved in boiling diethyl ether at 18
As a result of time extraction, the inaccuracy (hereinafter abbreviated as 11) is 97
,00/).

In addition, the melt index (ASTMD-1) of this polymer
238, measured at 190°C and a load of 2.16k9.

Hereinafter, it will be abbreviated as Ml2. ) was 0.379/10min. Example 2 a) Polymerization reaction All examples except that the solid catalyst component obtained in Example 1-C) was used, and 0.45 mm01 of triethylaluminum, 0.90 mm01 of diethylaluminum monotaloride, and 0.132 mm01 of methyl p-toluate were used. 1-d)
Polymerization of butene-1 was carried out using the same method and conditions.

(In this example, [/8=2, Kano/T1254, (])/
Ti=108, total organic acid ester/8-0.31, total organic acid ester/(01-0.16) 98.8
9 of white polybutene-1 was obtained, and the polymer production efficiency of this catalyst system was 247.0k9/9Ti. Moreover, I of this polymer is 96.8%, and Ml2 is 0.57g
/10min. Example 3a) Polymerization reaction Similarly to Example 2, using the solid catalyst component obtained in Example 1-c), 0.45 mm of triethylaluminum
I1 diethyl aluminum monochloride 0.225m
m01,. Polymerization of butene-1 was carried out under the same method conditions as in Example 11a) except that methyl p-toluate was changed to 0.132 mm01.

(In this example, (0/Koji 0.5, Kano/Ti=54, (
b)/Ti=27, total organic acid ester/tan-0.31,
Total organic acid ester/[0.63].

) 110.7 g of white polybutene-1 was obtained, and the polymer production efficiency of this catalyst was 276.8 kg/9Ti.

Also, this polymer has 96.90I) and MI2 of 0.6
It was 19/10 min.

Comparative Example 1 Example 2 except that the solid catalyst component obtained in Example 1-c) was used and diethylaluminum monochloride was not used.
Polymerization of butene-1 was carried out under the same method conditions.

(In this example, (auto)/8-0, 8/Ti = 54, and total organic acid ester/yen = 0.31.) White polybutene-1 with a weight of 59.59 was obtained. The polymer production efficiency was 1488 kνJTi. This polymer had an I] of 96.2% and an M2 of 0.639/10 min.

Comparative Example 2 Using the solid catalyst component obtained in Example 1-c), triethylaluminum 0.05mm011 diethylaluminum monochloride 0.75mm01. Butene-1 was polymerized under the same method conditions as in Example 1 except that methyl p-toluate was changed to 0.011T1rT101 (in this example, 01/Ko-15, 8/Ti-61101/Ti=9).
0, total organic acid esters/tan = 0.38 total organic acid esters/I) l-0.03.

) 47.49 white polybutene-1 was obtained, and the polymer production efficiency of this catalyst was 118.6k9/GTi.
of this polymer is 94.10/), MI2=0.949/
It was hot for 10 minutes. Example 4 Using the solid catalyst component obtained in Example 1-c), 0.45 mm of triethylaluminum, 0.225 mm of ethyl aluminum dichloride, . Butene-1 was polymerized under the same method conditions as in Example 1 except that methyl p-toluate was used in an amount of 0.08 mm01.

(0 in this example) 11/Ko=0.5, 5/Ti=54
, 01/Ti=27, total organic acid ester/8=0.20
1 total organic acid ester/I)l=0.40.

Claims (1)

[Claims] 1 Formula R^1aHbSio(4-a-b)/2 (however,
R^1 is selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an alloxy group, and a is 0
, an integer of 1 or 2, b represents 1, 2 or 3, a+
The reaction product (a) of a linear or cyclic hydropolysiloxane having a structural unit represented by (b≦3) and a Grignard reagent has the general formula R^2nM^(^Z^)Xr.
-n (However, in the formula, R^2 is a hydrocarbon group having 1 to 12 carbon atoms, M is an aluminum atom or a silicon atom, z represents the valence thereof and is a number of 3 or 4, and X is a halogen atom. , n represents a number from 0 to (z-1).) The reaction product (b) obtained by reacting one or more compounds represented by A solid catalyst component [A] obtained by reacting with one or more titanium halogen compounds, a trialkylaluminum compound [B], an organic acid ester [C] and the general formula AIR^3_mCl_3_-_m (wherein R ^3 is a hydrocarbon group having 1 to 8 carbon atoms, 0<m<3. ] and the trialkylaluminum compound [B] in a molar ratio within the range of 0.1 to 10.